Tip-enhanced Spectroscopy Research Articles

Fluorescence enhancement and quenching in tip-enhanced fluorescence spectroscopy

We study fluorescence enhancement for a dipole emitter placed between a tip and different dielectric substrates. Resonant behavior is observed as a function of tip-substrate distance for a silver tip placed above a glass substrate and displays a strong dependence on the radius of the curvature of the tip. By choosing appropriate sizes for the tip radius and the tip-substrate gap to optimize the competition between field enhancement and fluorescence quenching, we have found fluorescence enhancement exceeding three orders of magnitude can be achieved. The enhancement can be further improved by matching the silver tip with an appropriate dielectric substrate to resonantly excite gap plasmons. This is verified by comparing the matched silver tip-TiO2 substrate pairing with non-matched tip-dielectric substrate pairings. Compared with the large fluorescence enhancement observed in the case of a silver tip above a glass substrate, modest enhancement is obtained for a silicon tip and can be further improved by using a high dielectric material as the substrate. The optimal tip-enhanced fluorescence obtained in a silver tip-TiO2 substrate pairing may be useful in obtaining efficient fluorescence signal in the same setup used for tip-enhanced Raman spectroscopy.

Tip-Enhanced Second Harmonic Generation: an Approach for Hyper-Raman Spectroscopy

The near-field optical response generated at the apex of a scanning probe in tip-enhanced Raman spectroscopy (TERS) enhances and confines the interaction of light and matter to a few nanometers, thus breaking the diffraction limit of light while preserving the wealth of chemical and structural information. With the way paved to deploy Raman spectroscopy to surface nanostructures, we now investigate the most favorable experimental conditions and possible limitations for tip-enhanced hyper-Raman spectroscopy (TEHRS). In this two-photon-one phonon process, detected around the second harmonic of the excitation wavelength, selection rules different from those of the conventional Raman effect apply, thus holding promise for an almost comprehensive vibrational signature of the sample. TEHRS signal intensity critically depends on the second harmonic generation (SHG) efficiency. The aim of this work is to outline the experimental conditions that are best suited to obtain TEHRS signals in the challenging context of an extremely low scattering cross section. Using a silver tip and non-centrosymmetric PbTiO3 film on platinum substrate as a sample system in our simulations, we show a strong dependence of the intensity of SHG on the polarization of the incident light, the tip radius, the presence of a non-centrosymmetric sample, and the excitation power. We further discuss the effect of tip-sample distance for early-stage (proof of concept) TEHRS investigations and found 40% of total power dissipation for 1 nm distance.

Interactions of Silver Nanoparticles Formed in Situ on AFM Tips with Supported Lipid Bilayers.

A facile approach for functionalizing atomic force microscopy (AFM) tips with nanoparticles (NPs) will provide exciting opportunities in the field of tip-enhanced vibrational spectroscopy and in probing the interactions between NPs and biological systems. In this study, through successive exposure to polydopamine and AgNO3 solutions, the apex of AFM tips was functionalized with silver nanoparticles (AgNPs). The AgNP-modified AFM tips were used to measure the interaction forces between AgNPs and supported lipid bilayers (SLBs) formed on mica, as well as to probe the penetration of SLBs by AgNPs, with an emphasis on the effect of human serum albumin (HSA) proteins. AgNPs experienced predominantly repulsive forces when approaching SLBs. The presence of HSA resulted in an enhancement in the repulsive interactions between AgNPs and SLBs, likely through steric repulsion. Finally, the forces required for AgNPs to penetrate SLBs were higher in the presence of HSA probably due to the increase in the effective size of the nanoscale protuberances on the AFM tip stemming from the formation of protein coronas around the AgNPs.

Plasmon-Mediated Drilling in Thin Metallic Nanostructures.

Thin and ultraflat conductive surfaces are of particular interest to use as substrates for tip-enhanced spectroscopy applications. Tip-enhanced spectroscopy exploits the excitation of a localized surface plasmon resonance mode at the apex of a metallized atomic force microscope tip, confining and enhancing the local electromagnetic field by several orders of magnitude. This allows for nanoscale mapping of the surface with high spatial resolution and surface sensitivity, as demonstrated when coupled to local Raman measurements. In gap-mode tip-enhanced spectroscopy, the specimen of interest is deposited onto a flat metallic surface and probed by a metallic tip, allowing for further electromagnetic confinement and subsequent enhancement. We investigate here a geometry where a gold tip is used in conjunction with a silver nanoplate, thus forming a heterometallic platform for local enhancement. When irradiated, a plasmon-mediated reaction is triggered at the tip–substrate junction due to the enhanced electric field and the transfer of hot electrons from the tip to the nanoplate. This resulting nanoscale reaction appears to be sufficient to ablate the thin silver plates even under weak laser intensity. Such an approach may be further exploited for patterning metallic nanostructures or photoinduced chemical reactions at metal surfaces.

Directional surface plasmon-coupled emission of tilted-tip enhanced spectroscopy

Abstract Understanding the spatial radiation pattern in tip-enhanced spectroscopy (TES) is crucial for plasmon-enhanced spectroscopy, chemical analysis and biochemical sensing. Although the TES technique has many excellent advantages, there is still room for improvement in terms of detection sensitivity. In this paper, we theoretically demonstrate the tip-tilted TES configuration featuring high directivity by using side illumination-collection condition. Taking full advantage of the characteristic of high directional emission ascribed to the far-field interference between localized surface plasmon resonance (LSPR) and surface plasmon polariton (SPP) modes, the collection efficiency of TES signals can be largely improved, greatly boosting the detection sensitivity of TES technology. Our theoretical results not only provide a deep understanding of the underlying physical mechanism of the directional surface plasmon-coupled emission of TES, but also serves as a promising guide for the rational construction of a highly efficient TES platform at the single molecular level.

Field enhanced graphene based dual hexagonal ring optical antenna for tip-enhanced spectroscopy

Field enhanced graphene based dual hexagonal ring optical antenna has been designed in IR regime. Outcomes of hexagonal rings with gold and graphene materials and their effect has been studied and analyzed. Graphene based structures are found to have better and enhanced results as compared to that of gold. In addition, a two fold increase in bandwidth (∼30 THz) and cross-section (∼6.00E+06 nm2) has been observed in case of graphene. Field patterns for various tip/corner curvatures are simulated and localized/regional field patterns are justified. The effect of inter ring spacing on absorption cross section has been studied for every 10 nm increase in spacing. This absorption enhancement in addition to field localization makes the current structure feasible for tip enhanced spectroscopy.

Theoretical Localized Electric Field Enhancement in Tip-Enhanced Spectroscopy Using Multi-Order Radially Polarized Modes

Multi-order radially polarized modes (RPMs), including Bessel-Gaussian, Gaussian, Super Gaussian, and multi-order hollow Gaussian are respectively utilized as the illumination laser to achieve tip-enhanced spectroscopy (TES). Based on the vector diffraction theory and finite difference time domain (FDTD) analysis, we achieve the optimization of RPM illuminated TES system, including the focal spot size, focal depth, and electric field enhancement factor, in which the focal spot size of 5th order hollow Gaussian RPM is smallest (0.54λ) and the focusing depth of super Gaussian RPM is longest (4.71λ). Specially, it is found that the multi-order hollow Gaussian RPM illuminated TES system with the tip cone angle of 45° reveals better focusing ability and 40~60-fold electric field enhancement factor compared to the linearly polarized mode (LPM) illuminated TES system. These results will supply a useful reference for spectral signal enhancement of TES system.

Multianalytical approach for surface- and tip-enhanced infrared spectroscopy study of a molecule-metal conjugate: deducing its adsorption geometry.

This study presents a multianalytical approach for surface-enhanced infrared absorption spectroscopy (SEIRA) and tip-enhanced infrared nanospectroscopy (TEIRA) studies of the α-methyl-dl-tryptophan adsorption geometry on a gold nanoparticle surface. Comparison of SEIRA spectra obtained in the transmission, attenuated total reflection and reflection modes verified the reproducibility of the adsorption. The application of the AutoSeagull (Harrick Scientific) accessory enabled us to track the dependence of the incident angle on the relative band intensity in the same area of the sample. Furthermore, the effect of two polarization modulations (p and s) in TEIRA was examined to deduce the adsorption geometry and to better understand the molecule/metal interaction. The nanogap between a gold-coated atomic force microscopy (AFM) tip and the gold surface induced electromagnetic enhancement in the optical field intensity. This is associated with the additional near-field electromagnetic field trapping effect. The local field intensity reinforcement significantly increased the infrared absorption cross-section of the compound under the tip with simultaneous improvement in spatial resolution. The originality of this study lies in the combination of various measurement modes and incident angles in SEIRA and two orthogonal polarizations in TEIRA to provide comprehensive characterization of the adsorption phenomenon. The results give important insights into tracking subtle changes in molecule geometry upon adsorption.

Probing the nanoscale light emission properties of a CVD-grown MoS2 monolayer by tip-enhanced photoluminescence.

Two-dimensional transition metal dichalcogenides are gaining increasing interest due to their promising optical properties. In particular, molybdenum disulfide (MoS2) which displays a band-gap change from indirect at 1.29 eV for bulk materials to direct at 1.8 eV for the material monolayer. This particular effect can lead to a strong light interaction which can pave the way for a new approach to the next generation of visible light emitting devices. In this work we show the nanoscale variation of light emission properties by tip-enhanced photoluminescence microscopy and spectroscopy in the MoS2 monolayer, grown by chemical vapour deposition. The variations of the light emission properties are due to different effects depending on the shape of the MoS2 single layer, for instance, a different concentration of point defect in an irregularly shaped flake and the presence of a nanoscale terrace in a triangular monolayer. Simultaneously, atomic force microscopy reveals indeed the presence of a nanometric terrace, composed of an additional layer of MoS2, and tip-enhanced PL intensity imaging shows a localized intensity decrease.

Tip-enhanced photoluminescence spectroscopy of monolayer MoS_2

Probing the optical properties of molybdenum disulfide (MoS2) is vital to its application in plasmon-enhanced spectroscopy, catalysts, sensing, and optoelectronic devices. In this paper, we theoretically studied the Raman and fluorescence properties of monolayer MoS2 using tip-enhanced spectroscopy (TES). In the strong-coupling TES system, the Raman and fluorescence enhancement factors can be turned to as high as 4.5×108 and 3.3×103, respectively, by optimizing the tip–MoS2-film distance. Our theoretical results not only help to deeply understand the TES properties of monolayer MoS2, but also provide better guidance on the applications of the novel two-dimensional material.

Chemical Nano-Imaging with Tip-Enhanced Vibrational Spectroscopy

Chemical Nano-Imaging with Tip-Enhanced Vibrational Spectroscopy

Nanofabrication of the gold scanning probe for the STM-SECM coupling system with nanoscale spatial resolution

Scanning probe is the key issue for the electrochemical scanning probe techniques (EC-SPM) such as EC-scanning tunnel microscopy (STM), EC-atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM), especially the insulative encapsulation of the nanoelectrode probe for both positioning and electrochemical feedbacks. To solve this problem, we develop a novel fabrication method of the gold nanoelectrodes: firstly, a micropipette with nanomter-sized orifice was prepared as the template by a laser puller; secondly, the inside wall of micropipette apex was blocked by compact and conic Au nano-piece through electroless plating; thirdly, the Au nano-piece was grown by bipolar electroplating and connected with a silver wire as a current collector. The fabricated Au nanoelectrode has very good voltammetric responses for the electrodic processes of both mass transfer and adsorption. The advantage lies in that it is well encapsulated by a thin glass sealing layer with a RG value lowered to 1.3, which makes it qualified in the SECM-STM coupling mode. On one hand, it can serve as STM tip for positioning which ensures the high spatial resolution; on the other hand, it is a high-quality nanoelectrode to explore the local chemical activity of the substrate. The nanofabrication method may promote the SPM techniques to obtain simultaneously the physical and chemical images with nanoscale spatial resolution, which opens a new approach to tip chemistry in electrochemical nanocatalysis and tip-enhanced spectroscopy.

Near-Field Raman Spectroscopy with Aperture Tips.

In this paper, we review nano-Raman techniques based on aperture scanning near-field optical microscopy (SNOM). Fundamentals of SNOM and aperture-tip-based near-field Raman spectroscopy and their applications in key technical issues, including Raman signal intensity and collection time, are introduced. Recent advances in the tip design are discussed, and applications of the aperture-SNOM-based nano-Raman technique are presented. We attempt to identify the most pressing open questions in this field. We believe that, by improving the power transmission efficiency and combining the local field enhancing technique with the tip-enhanced spectroscopy, the performance of aperture-SNOM can be significantly improved. Its nanometer-scale excitation volume and the consequent low background make the aperture-tip technique feasible for many important samples that cannot be measured by other optical nanospectroscopies.

Directionally enhanced probe for side-illumination Tip enhanced spectroscopy

We demonstrate a high-performance apertureless near-field probe made of a tapered metal tip with a set of periodic shallow grooves near the apex. The spontaneous emission from a single emitter near the tip is investigated systematically for the side-illumination tip enhanced spectroscopy (TES). In contrast with the bare tapered metal tip in conventional side-illumination TES, the corrugated probe not only enhances strongly local excitation field but also concentrates the emission directivity, which leads to high collection efficiency and signal-to-noise ratio. In particular, we propose an asymmetric TES tip based on two coupling nanorods with different length at the apex to realize unidirectional enhanced emission rate from a single emitter. Interestingly, we find that the radiation pattern is sensitive to the emission wavelength and the emitter positions respective to the apex, which can result in an increase of signal-to-noise ratio by suppressing undesired signal. The proposed asymmetrical corrugated probe opens up a broad range of practical applications, e.g. increasing the detection efficiency of tip enhanced spectroscopy at the single-molecule level.

Nanostar probes for tip-enhanced spectroscopy

To overcome the current limit of tip-enhanced spectroscopy that is based on metallic nano-probes, we developed a new scanning probe with a metallic nanostar, a nanoparticle with sharp spikes. A Au nanoparticle of 5 nm was first attached to the end of a tip through DNA-DNA hybridization and mechanical pick-up. The nanoparticle was converted to a nanostar with a core diameter of ∼70 nm and spike lengths between 50 nm and 80 nm through the reduction of Au(3+) with ascorbic acid in the presence of Ag(+). Fabrication yields of such tips exceeded 60%, and more than 80% of such tips showed a mechanical durability sufficient for use in scanning microscopy. Effectiveness of the new probes for tip-enhanced Raman scattering (TERS) and tip-enhanced fluorescence (TEF) was confirmed. The probes exhibited the necessary enhancement for TEF, and the tip-on and tip-off ratios varied between 5 and 100. This large tip-to-tip variability may arise from the uncontrolled orientation of the apexes of the spike with respect to the sample surface, which calls for further fabrication improvement. The result overall supports a new fabrication approach for the probe that is effective for tip-enhanced spectroscopy.

Revealing nanoscale optical properties and morphology in perfluoropentacene films by confocal and tip-enhanced near-field optical microscopy and spectroscopy.

Combining high resolution optical microscopy and spectroscopy, we propose a novel, generally applicable and highly sensitive method for determining the local morphology in organic semiconductor thin films (e.g. perfluoropentacene (PFP)). An azimuthally or radially polarized doughnut mode (APDM or RPDM) laser beam is focused by a high numerical aperture parabolic-mirror to excite a diffraction limited volume of the PFP film with an electric field polarized either exclusively in-plane or dominantly out-of-plane (relative to the substrate). We find two distinct morphologies of thin PFP films: molecular aggregates and crystalline terraces. The well-defined dipole emission patterns observed from the molecular aggregates strongly suggest the presence of localized excitations. For both laser modes, we observe that for the PFP aggregates, the photoluminescence (PL) emission from the main electronic transition is blue-shifted by about 10 meV, as compared to that from the molecular terraces. For the C-C bending modes, the B3g at 1581 cm(-1) (ν1) and the Ag at 1316 cm(-1) (ν0), we observe a decrease of the intensity ratio (Iν1/Iν0) from 0.6 (terrace) to 0.15 (aggregate). Furthermore, the intensity ratios (IAPDM/IRPDM) of ν1 excited by different polarizations increase from 0.12 (terrace) to 0.73 (aggregate). These results indicate that the PFP molecules orient rather parallel to the substrate in the aggregates, whilst more upright in the terraces. Benefiting from the nanometer scale optical resolution offered by the tip-enhanced near-field optical method, we observe clear optical contrasts between the molecular aggregate and the terrace as well as individual layers within a terrace. Tip-enhanced optical spectra locally taken from the molecular terrace and the aggregate show similar blue-shift of the main PL peak and change in the Raman intensity with different polarizations as from the far-field assemble-measurements, which further confirms the different molecular orientations in these two morphologies.

Effect of electric field gradient on sub-nanometer spatial resolution of tip-enhanced Raman spectroscopy.

Tip-enhanced Raman spectroscopy (TERS) with sub-nanometer spatial resolution has been recently demonstrated experimentally. However, the physical mechanism underlying is still under discussion. Here we theoretically investigate the electric field gradient of a coupled tip-substrate system. Our calculations suggest that the ultra-high spatial resolution of TERS can be partially attributed to the electric field gradient effect owning to its tighter spatial confinement and sensitivity to the infrared (IR)-active of molecules. Particularly, in the case of TERS of flat-lying H2TBPP molecules,we find the electric field gradient enhancement is the dominating factor for the high spatial resolution, which qualitatively coincides with previous experimental report. Our theoretical study offers a new paradigm for understanding the mechanisms of the ultra-high spatial resolution demonstrated in tip-enhanced spectroscopy which is of importance but neglected.

Model for quantitative tip-enhanced spectroscopy and the extraction of nanoscale-resolved optical constants

Near-field infrared spectroscopy by elastic scattering of light from a probe tip resolves optical contrasts in materials at dramatically sub-wavelength scales across a broad energy range, with the demonstrated capacity for chemical identification at the nanoscale. However, current models of probe-sample near-field interactions still cannot provide a sufficiently quantitatively interpretation of measured near-field contrasts, especially in the case of materials supporting strong surface phonons. We present a model of near-field spectroscopy derived from basic principles and verified by finite-element simulations, demonstrating superb predictive agreement both with tunable quantum cascade laser near-field spectroscopy of SiO$_2$ thin films and with newly presented nanoscale Fourier transform infrared (nanoFTIR) spectroscopy of crystalline SiC. We discuss the role of probe geometry, field retardation, and surface mode dispersion in shaping the measured near-field response. This treatment enables a route to quantitatively determine nano-resolved optical constants, as we demonstrate by inverting newly presented nanoFTIR spectra of an SiO$_2$ thin film into the frequency dependent dielectric function of its mid-infrared optical phonon. Our formalism further enables tip-enhanced spectroscopy as a potent diagnostic tool for quantitative nano-scale spectroscopy.

Directional and enhanced spontaneous emission with a corrugated metal probe.

A three-dimensional corrugated metal tapered probe with surface corrugated gratings at the tip apex is proposed and investigated theoretically, which leads to an obvious emission beaming effect of spontaneous emission from a single emitter near the probe. In contrast with conventional apertureless metal probes, where only the enhancement of an optical near-field is concerned, the corrugated probe is able to manipulate local excitation intensity and far-field emission direction simultaneously. The angular emission from a single dipole source, being placed close to the corrugated probe, falls into a cone with a maximum directivity angle of ±11.6°, which improves the collection efficiency 25-fold. Such a probe simultaneously increases the localized field intensity to about twice as strong as the conventional bare tip. In addition, the radiation pattern is sensitive to the working wavelength and the dipole to tip-apex separation. These findings make a promising route to the development of plasmonic spontaneous emission manipulation based on corrugated tapered antenna-for instance, tip-enhanced spectroscopy, single-molecule sensing, and single-photon source.

A cryogenic scattering-type scanning near-field optical microscope

Scattering-type scanning near-field optical microscopy (s-SNOM) provides few nanometer optical spatial resolution and is compatible with nearly any form of linear and nonlinear optical spectroscopy. We have developed a versatile s-SNOM instrument operating under cryogenic and variable temperature (∼20-500 K) and compatible with high magnetic fields (up to 7 T). The instrument features independent tip and sample scanning and free-space light delivery with an integrated off-axis parabolic mirror for tip-illumination and signal collection with a numerical aperture of N.A. = 0.45. The optics operate from the UV to THz range allowing for continuous wave, broadband, and ultrafast s-SNOM spectroscopy, including different variants of tip-enhanced spectroscopy. We discuss the instrument design, implementation, and demonstrate its performance with mid-infrared Drude response s-SNOM probing of the domain formation associated with the metal-insulator transitions of VO2 (TMIT ≃ 340 K) and V2O3 (TMIT ≃ 150 K). This instrument enables the study of mesoscopic order and domains of competing quantum phases in correlated electron materials over a wide range of controlled electric and magnetic fields, strain, current, and temperature.